Process for polymerizing olefins and catalyst therefor

ABSTRACT

1. IN A PROCESS FOR POLYMERIZING OR COPOLYMERIZING A MONOMER SELECTED FROM THE GROUP CONSISTING OF ETHYLENE, PROPYLENE, 1-BUTENE, 4-METHYL-1-PENTENE, STYRENE, 1-PENTENE, 1-HEXENE AND 3-METHYL-1-BUTENE IN THE PRESENCE OF A CATALYST COMPOSED OF A PULVERIZED TITANIUM TRICHLORIDE COMPONENT AND AN ORGANO-ALUMINUM COMPOUND, THE IMPROVEMENT WHEREIN SAID MONOMER IS POLYMERIZED OR COPOLYMERIZED IN THE PRESENCE OF A CATALYST COMPRISING: (A) A TITANIUM TRICHLORIDE COMPOSITION OBTAINED BY PULVERIZING A COMPONENT CONSISTING OF AN ALUMINUMCONTAINING TITANIUM TRICHLORIDE COMPONENT PREPARED BY THE REDUCTION OF TITANIUM TETRACHLORIDE WITH METALLIC ALUMINUM, UNTIL THE A- OF V-TYPE CRYSTAL STRUCTURE OF TITANIUM TRICHLORIDE CANNOT BE IDENTIFIED IN THE X-RAY DIFFRACTION PATTERN, AND EXTRACTING THE RESULTING TITANIUM TRICHLORIDE COMPOSITION WITH A SOLVENT MIXTURE OF AN INERT ORGANIC SOLVENT: (1) SELECTED FROM THE GROUP CONSISTING OF AROMATIC HYDROCARBONS HAVING 6 TO 20 CARBON ATOMS, SATURATED ALIPHATIC HYDROCARBONS HAVING 3 TO 20 CARBON ATOMS, ALICYCLIC HYDROCARBONS HAVING 3 TO 18 CARBON ATOMS, ACYCLIC OR CYCLIC OLEFINS OF 2 20 CARBON ATOMS, UNSATURATED ALIPHATIC HYDROCARBON HALIDES OF 2 TO 20 CARBON ATOMS, SATURATED ALIPHATIC HYDROCARBON HALIDES OF 1 TO 20 CARBON ATOMS, HALOGENATED HALIDES HYDROCARBONS HAVING 6 TO 16 CARBON ATOMS AND CARBON DISULFIDE; AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE FOLLOWING ORGANIC SOLVENTS; (2) AN OXYGEN-CONTAINING ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF SATURATED ALIPHATIC MONOETHERS HAVING 2 TO 32 CARBON ATOMS HAVING AN ALKYL RADICAL, APHATIC ETHERS OF 3 TO 20 CARBON ATOMS HAVING AT LEAST ONE UNSATURATED ALIPHATIC HYDROCARBON RADICAL, AROMATIC ETHERS OF 7 TO 16 CARBON ATOMS HAVING A SATURATED ALKYL OR ARYL RADICAL, MONOETHERS AND DIETHERS OF 7 TO 16 CARBON ATOMS WHICH ARE HALOGENATED AND CONTAIN AT LEAST ONE AROMATIC RADICAL, SATURATED ALKYL ESTERS OF SATURATED ALIPHATIC MONOCARBOXYLIC ACIDS HAVING AN ALIPHATIC MONOCARBOXYLIC ACID RESIDUAL GROUP WITH 1 TO 21 CARBON ATOMS AND A SATURATED ALKYL GROUP WITH 1 TO 16 CARBON ATOMS, UNSATURATED ALKYL ESTERS OF SATURATES ALIPHATIC MONOCARBOXYLIC ACIDS HAVING A SATURATED ALIPHATIC MONOCARABOXYLIC ACID RESIDUAL GROUP WITH 1 TO 8 CARBON ATOMS AND AN UNSATURATED ALKYL GROUP WITH 2 TO12   CH3SICH2((CH3)2SICH2)XSI(CH3)3   WHEREIN X IS AN INTEGER OF 1 TO 10, LINEAR POLYALKYL OR POLYARYL POLYSILANES OF 6 TO 80 CARBON ATOMS, A, Y-DIHALOALKYLPOLYSILOXANES OF THE FORMULA   X(R2SIO)XSIR2X   WHEREIN X IS A HALOGEN ATOMS, AND X=1, TO 1000, POLYALKYL CYCLOPOLYSILANES HAVING 12 TO 120 CARBON ATOMS, POLYARYL CYCLOPOLYSILANES HAVING 12 TO 120 CARBON ATOMS, ORGANOPOLYSILOXANES OF THE FORMULA   R(R&#39;&#39;R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39;SIO)XSIR3   WHEREIN R, R&#39;&#39; AND R&#39;&#39;&#39;&#39;&#39;&#39; MAY BE THE SAME OR DIFFERNET AND REPRESENT AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, AN ARYL GROUP HAVING 6 TO 8 CARBON ATOMS, OR HYDROGEN, AND X IS AN INTEGER OF 1 TO 1000, ALKYL CYCLOPOLYSILOXANES OF THE FORMULA   (R&#39;&#39;&#39;&#39;&#39;&#39;2SIO)Z   WHEREIN R&#39;&#39;&#39;&#39;&#39;&#39; IS AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, AND Y IS AN INTEGER OF 3 TO 8, ALKYL CYCLOPOLYSILOXANES OF THE GENERAL FORMULA   (R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39;2SIO)Z   WHEREIN R&#39;&#39;&#39;&#39;&#39;&#39; IS AN ALKYL GROUP HAVING 1 TO 4 CARBON ATOMS, AND Z IS AN INTEGER OF 3 TO 9, ATOMS, AND Z IS AN INTEGER OF 3 TO 9, ARYL CYCLOOPOLYSILOXANES OF THE FORMULA   12 ARBON ATOMS, ALKYL ESTERS OF UNSATURATED ALIPHATIC MONOCARBOXYLIC ACIDS HAVING AN UNSATURATED ALIPHATIC MONOCARBOXYLIC ACID RESIDUAL GROUP WITH 2 TO 12 CARBON ATOMS AND A SATURATED OR UNSATURATED ALKYL GROUP WITH 1 TO 10 CARBON ATOMS, SATURATED ALKYL ESTERS OF AROMATIC MONOCARBOXYLIC ACIDS HAVING AN AROMATIC MONOCARBOXYLIC ACID RESIDUAL GROUP WITH 7 TO 18 CARBON ATOMS AND A SATURATED ALKYL GROUP WITH 1 TO 20 CARBON ATOMS, SATURATED ALIPHATIC MONOALCOHOLS HAVING 1 TO 18 CARBON ATOMS, MONOHYDRIC AND DIHYDRIC PHENOLS HAVING 6 TO 16 CARBON ATOMS, SATURATED ALIPHATIC MONOKETONES HAVING 3 TO 20 CARBON ATOMS, SATURATED ALIPHATIC DIKETONES HAVING 4 TO 12 CARBON ATOMS, AROMATIC MONOKETONES HAVING 7 TO 18 CARBONS ATOMS, AROMATIC MONOCARBOXYLIC ACID HAVING 7 TO 18 CARBON ATOMS, SATURATED ALIPHATIC MONOCARBOXYLIC ACIDS HAVING 1 TO 20 CARBON ATOMS, SATURATED ALIPHATIC CARBOXYLIC ACID HALIDES HABIHAVING 2 TO 12 CARBON ATOMS AND AROMATIC CARBOXYLIC ACID HALIDES HAVING 7 TO 15 CARBON ATOMS; (2)&#39;&#39; A NITROGEN-CONTAINING ORGANIC SOLVENT SELECTE D FROM THE GROUP CONSISTING OF NITROGEN-CONTAINING HETEROCYCLIC AMINES HAVING 5 TO 18 CARBON ATOMS SELECTED FROM THE PYRIDINE, QUINOLINE AND ACRIDINE SERIES, SATURATED ALIPHATIC SECONDARY AMINES OF 2 TO 24 CARBON ATOMS, AROMATIC SECONDARY AMINES HAVING 6 TO 20 CARBON ATOMS, SATURATED ALIPHATIC TERTIARY AMINES HAVING 3 TO 18 CARBON ATOMS, AROMATIC TERTIARY AMINES HAVING 8 TO 30 CARBON ATOMS, AROMATIC MONONITRILES HAVING 7 TO 15 CARBON ATOMS, AROMATIC MOMOISOCYANATES HAVING 7 TO 11 CARBON ATOMS AND AROMATIC AZO COMPOUNDS HAVING 12 TO 20 CARBON ATOMS; AND (2)&#39;&#39;&#39;&#39; A SI-CONTAINING ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF TETRAHYDROCARBYLISILANES HAVING SATURATED ALKYL RADICALS, ARYL RADICALS OR MIXTURES THEREOF OF 4 TO 5O CARBON ATOMS, TETRAHYDROCARBYLSILANES HAVING AN UNSATURATED ALKYL RADICAL OF 5 TO 28 CARBON ATOMS, ALKYL HYDROGENOSILANES OF 1 TO 30 CARBON ATOMS, HAVING AN SI-H BONDS, ARYL HYDROGENOLSILANES OF 6 TO 30 CARBON ATOMS HAVING AN SI-H BOND, ALKYL HALOGENOSILANES OF 3 TO 30 CARBON ATOMS HAVING AN SI-HALOGEN BOND, ARYL HALOGENOSILANES OF 6 TO 30 CARBON ATOMS HAVING AN SI-HALOGEN BOND, TRIALKYL SILYLAMINES OF 6 TO 9 CARBON ATOMS, TRIPHENYL SILYLAMINE, TRIMETHYL(N - METHYLAMINO) SILANE, TRIMETHYL (N - DIETHYLAMINO) SILANE, SATURATED ALKYLSILANES HAVING AT LEAST ONE SI-O-C BONDS OF 2 TO 8 CARBON ATOMS, ARYL SILANES HAVING AT LEAST AN SI-O-C BOND OF 9 TO 12 CARBON ATOMS, C1-C10 ALIPHATIC MONO-OR C7-C11 AROMATIC MONO-CARBOXYLIC ACID ESTERS OF TRIALKYL SILANOLS HAVING 3 TO 10 CARBON ATOMS, ALKYLARYL SILANOLS HAVING 8 TO 20 CARBON ATOMS OR TRIARYL SILANOLS 18 TO 30 CARBON ATOMS, TRIALKYL SILICON ISOCYANATES HAVING 3 TO 10 CARBON ATOMS, DIALKYL ARYL SILICON ISOCYANATES HAVING TO 15 CARBON ATOMS, TRIALKYL SILICON ISOCYANATES HAVING 18 TO 30 CARBON ATOMS, POLYSILMETHYLENES OF THE FORMULA (Q2SIO)P WHEREIN Q IS AN ARYL GROUP HAVING 6 TO 8 CARBON ATOMS, AND P IS AN INTEGER OF 3 TO 6, ALKYL OR ARYL POLYSILAZANES OF 6 TO 50 CARBON ATOMS HAVING AN SI-NI-SI BOND AND A MOLECULAR WEIGHT OF NOT MORE THAN 100; AND THEN SEPARATING SAID EXTRACTED TITANIUM TRICHLORIDE COMPOSITION FROM THE SOLVENT MIXTURE, THE AMOUNT OF SAID MIXED SOLVENT BEING 1 TO 100 PARTS BY WEIGHT PER PART OF THE PULVERIZED ALUMINUM-CONTAINING TITANIUM TRICHLORIDE COMPONENT, AND THE AMOUNT OF THE SOLVENT (2) OR (2)&#39;&#39;&#39;&#39; BEING 0.00510.0 PARTS BY WEIGHT PER PART OF SAID TITANIUM TRICHLORIDE COMPONENT AND THE AMOUNT OF SOLVENT (2)&#39;&#39; BEING 0.O05-0.5 PART BY WEIGHT PER PART OF SAID TITANIUM TRICHLORIDE COMPONENET; AND (B) AN ORGANOALUMINUM COMPOUND SELECTED FROM THE GROUP CONSISTING OF TRIALKYL ALUMINUM, DIALKYLALAUMINUM HALIDE, DIALKYLALUMINUM ALKOXIDE, ALKYALUMINUM ALKOXY HALIDE, REACTION PRODUCTS OF THESE WITH AN ELECTRON-DONOR COMPOUND, REACTION PRODUCTS OF THESE WITH AN ALKALI METAL COMPLEX FLUORIDE OF A TRANSITION METAL, REACTION PRODUCTS OF AN ALKYLALUMINUM DIHALIDE WITH AN ELECTRON-DONOR COMPOUND, REACTION PRODUCTS OF AN ALKYLALUMINUM DIHALIDE WITH AN ALKALI METAL HALIDE, AND REACTION PRODUCTS OF AN ALKYLALUMINUM DIHALIDE WITH AN ALKALI METAL COMPLEX FLUORIDE OF A TRANSITION METAL.

United States Patent 3,850,899 PROCESS FOR POLYMERIZING OLEFINS ANDCATALYST THEREFOR Shigeru Wada, Otake, Hidesaburo 0i, Yamaguchi-ken,Norio Matsuzawa and Hiroshi Nishimura, Otalre, and .l'untaro Sasaki,Iwakuni, Japan, assignors to Mitsui Petrochemical Industries, Ltd.,Tokyo, Japan No Drawing. Filed June 14, 1971, Ser. No. 153,014 Claimspriority, application Japan, June 15, 1970, 45/514154; July 17, 1970,45/452,301, 45/62,302 Int. Cl. B011 11/84; C08f 1/56 U.S. Cl. 26088.2 R2 Claims ABSTRACT OF THE DISCLOSURE In a process for polymerizingalpha-olefins in the presence of a catalyst composed of a pulverizedtitanium trichloride component and an organoaluminum compound, theimprovements wherein an alpha-olefin is polymerized in the presence of acatalyst comprising (A) and (B) below:

(A) A titanium trichloride composition obtained by pulverizing analuminum-containing titanium trichloride component prepared by thereduction of titanium tetrachloride with metallic aluminum, in theabsence of an auxiliary component and without adding an aluminumtrihalide or antimony trihalide, until the uor 'y-type crystal type ofthe titanium trichloride cannot be identified in the X-ray dilfractionpattern, and extracting the resulting titanium trichloride compositionwith a solvent mixture of an inert organic solvent and a member selectedfrom the group consisting of an oxygen-containing organic solvent, anitrogen-containing organic solvent and Si-containing oragnic solvent;and

(B) An organoaluminum compound.

This invention relates to an improvement of a catalyst for use in thepolymerization of u-olefins, and more specifically to a process forpreparing a homoor copolymer of a-olefins by using a catalyst whichexhibits sufficiently high polymerizing activity in the polymerizationof aolefins such as propylene and l-butene to form a stereospecificpolymer.

The Ziegler-Natta catalysts have been well known as catalysts forpreparing stereospecific polymers of a-olefins such as propylene, 1butene, 4 methyl-l-pentene or styrene. The most typical of suchcatalysts is a system composed of a titanium halide and atriethylaluminum or diethylaluminum halide. It is also well known thatwhen a-olefins are polymerized using these catalyst systems,stereospecific polymers can be obtained. It is known however thatattempts to increase the polymerization activity of the Ziegler-Nattacatalysts generally result in a drastic decrease in the crystallinity ofthe resultant ocolefin polymer and consequently, an increased amount ofan amorphous polymer. The titanium halides now in wide spread use aretitanium trichloride compositions, which are produced by (a) reductionof titanium tetrachloride with metallic aluminum, followed bypulverization in a dry condition to activate it, (b) reduction oftitanium tetrachloride with hydrogen or metallic titanium, followed bypulverization, or (c) reduction of titanium tetrachloride with anorgano-aluminum compound.

However, stereospecific polymerization of u-olefins using a catalystconsisting of a titanium trichloride composition so prepared and anorganoaluminum compound results in the formation of great quantities ofan amorphous polymer. Usually, therefore, the manufacturing process forstereospecific polymers of a-olefins such as polypropylene involves astep of separating the amorphous polymer.

In the commercial production of typical a-olefin polymers such aspolypropylene, poly-l-butene, or poly-4- methyl-l-pentene, increasingthe amount of polymer formed per unit amount of catalyst and theminimizing the amount of amorphous polymer are the very importantconsiderations. With increasing amounts of polymer formed per unitamount of catalyst, the amount of catalyst used and can be less, and thecatalyst remaining in the polymer can be removed more easily.Consequently, the amount of inorganic component contained in the productis reduced, and the quality of the product can be improved with respectto rust occurrence, color, fish eye, weatherability, transparency andinsulating property. This also enables the catalyst preparation step,ash removing step, amorphous polymer separating step, etc. in theprocess of producing polymers to be simplified and to be even omitted inthe case of the latter two steps, and results in a curtailment of theplant constructing cost and the cost of production of polymers.

The non-crystalline polymer formed in the polymerization of u-olefinsnot only makes the operation of the manufacturing plant complicated, butis totally useless. Such polymer is discarded without utilization, andcauses a high price for the stereospecific polymer product. Under thecircumstances, therefore, the development of catalysts having highactivity and capable of giving highly stereospecific polymers has beendesired.

In general, a titanium trichloride composition obtained by reducingtitanium tetrachloride with hydrogen, titanium metal, or aluminum metalhas low activity for aolefins, and gives polymers of insufiicientcrystallinity. With a view to increasing the activity of such catalyst,a method of pulverizing a titanium trichloride composition with avibratory mill or dry ball mill has been proposed (British Pat. 850,910and U.S. Pat. 3,032,510).

According to this proposal, the polymerization activity may be increasedby the pulverizing treatment, but the crystallinity of the polymerrather tends to be on a decrease. As a result, the stereospecificity ofthe activated catalyst is worsened, and a great amount of an amorphouspolymer is formed.

Another proposal in this line is to reduce titanium tetrachloride with ametal such as aluminum in the presence of an amine, ether or ketone toform a complex compound with aluminum chloride formed, and wash it withan inert solvent, amines or ethers to remove aluminum chloridecompletely (French Pat. No. 1,315,782). The method proposed is intendedto inhibit the formation of an amorphous polymer by removing aluminumchloride in the titanium trichloride composition which is a cause of theformation of the amorphous polymer. Furthermore, owing to severereaction conditions due to the presence of the amines, ethers orketones, reaction takes place between the resulting titanium trichlorideand these additional compounds, and the polymerization activity of thecatalyst and its ability to form a stereospecific ploymer tend to bereduced. It is also usual that the performance of the titaniumtrichloride catalyst produced under such severe conditions is inferiorto that of a titanium trichloride composition activated bypulverization. Another disadvantage of this proposal is that theperformance of the catalyst is markedly reduced unless the resultingaluminum trichloride complex is completely removed.

On the other hand, US. Pat. 3,032,510 discloses that titaniumtetrachloride is reduced with metallic aluminum in the presence of anaromatic hydrocarbon such as benzene and toluene, the resulting titaniumtrichloride is recovered and pulverized, and the pulverized titaniumtrichloride is used as a component of the catalyst. This method may leadto an improved polymerization activity,

3 but meets with difficulty in inhibiting the formation of an amorphouspolymer.

It is also known that some of the compounds (2), (2), (2)", and (2)" tobe later described often contribute to an increase in the polymerizationactivity of the catalyst and/ or the crystallinity of the resultingpolymer when used in the polymerization system. But the time ofutilizing these compounds quite differs from that in the presentinvention, and the increase is only to an unsatisfactory degree. Withthese compounds, it is impossible to achieve a remarkable improvement asin the present invention.

It has now been found that stereospecific polymers of a-olefins can beproduced with convenient inhibition of the formation of amorphouspolymers using a catalyst having superior polymerization activity whichcomprises an organoaluminum compound and a titanium trichloridecomposition obtained by pulverizing an aluminum-containing titaniumtrichloride component prepared by the reduction of titaniumtetrachloride with metalic aluminum in the absence of the auxiliarycomponent and without adding an aluminum trihalide or antimony trihalideuntil the 00- or 'y-type of the X-ray diffraction pattern of the crystalform of the titanium trichloride cannot be identified, and extractingthe resulting titanium trichloride composition with a particular solventmixture.

The process of the invention has the advantage that a wide range ofmixed solvents can be used.

Accordingly, an object of the invention is to provide a process forpolymerizing olefins of even more improved crystallinity and a catalysttherefor which exhibits a remarkably increased polymerization activity.

Many other objects and advantages of the invention will become moreapparent from the following description.

The process of the invention is differentiated from the first priorproposal given above in that the titanium trichloride component is notone merely pulverized, from the second proposal in that thepulverization must be carried out in the absence of an auxiliarycomponent until the OL- or 'y-type of the X-ray diffraction pattern ofthe crystal form of titanium trichloride cannot be identified as thesame and extracting the resulting titanium trichloride with a mixedsolvent, and also from the third proposal in that titanium trichloridemust be pulverized in the absence of an auxiliary component and thepulverizedproduct must be extracted with a mixed solvent. In the presentinvention, the combination of the aforementioned conditions isessential, and omission of any of such conditions in following priorproposals does not bring about the superior improved effect of theinvention. This will be made clearer from the examples and comparativeexamples which appear later in the specification.

In the present invention, the titanium trichloride component obtained bypulverizing an aluminum-containing titanium trichloride componentprepared by the reduction of titanium tetrachloride with metallicaluminum is prepared in a manner well known in the art.

In the preparation of the catalyst of the invention, thealuminum-containing titanium trichloride is first pulverized in theabsence of an auxiliary component until the aor y-type of the X-raydiffraction pattern of the crystal form of the titanium trichloridecannot be identified. In the invention the pulverization is effected inthe absence of the auxiliary component and without adding an aluminumtrihalide. It should be noted that the objects of the present inventioncannot be achieved even if only a step of extracting and washingtitanium trichloride with mixed solvent is carried out with the omissionof the pulverizing step. The extraction step must be carried out with asolvent mixture of inert organic solvent (1) and another solvent (2),(2) or (2).

A very wide range of compounds are used as an inert organic solvent (1)Which is one component of the solvent mixture.

These are inert organic solvents selected from the group consisting ofaromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons,halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbonsand carbon disulfidc.

Solvents (2'), (2) or (2) which are another component of the solventmixture are:

(2) An oxygen-containing organic solvent selected from the groupconsisting of aliphatic ethers, aromatic ethers, aliphatic carboxylicacid esters, aromatic carboxylic acid esters, aliphatic alcohols,aliphatic aldehydes, aromatic aldehydes, aliphatic carboxylic acids,aromatic carboxylic acids, aliphatic carboxylic acid halides, aromaticcarboxylic acid halides, aliphatic ketones, aromatic ketones andphenols;

(2) A nitrogen-containing organic solvent selected from the groupconsisting of nitrogen-containing heterocyclic compounds, aliphaticsecondary amines, aromatic secondary amines, aliphatic tertiary amines,aromatic tertiary amines, aromatic nitriles, aromatic isocyanates andaromatic azo compound; and

(2) Si-containing organic solvent selected from the group consisting oftetrahydrocarbyl silanes, organohydrogenosilanes, organohalogenosilanes,alkoxy silanes, aryloxy silanes, silanol carboxylates, straight chainsiloxanes, cyclic polysiloxanes, aminosilanes, silazanes and isocyanatesilanes.

Examples of the above inert organic solvent (1) include the following:

Saturated aliphatic hydrocarbons of 3-20 carbon atoms such as propane,butane, pentane, hexane, 3-methylpentane, 2,3-dimethylbutane, n-heptane,2-methylhexane, n-octane, iso-octane, n-decane, n-dodecane, heptadecane,n-eicosane and kerosene;

Alicyclic hydrocarbons of 3-18 carbon atoms such as cyclopropane,cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane anddicyclohexyl; methylcyclopropane, ethylcyclobutane, methylcyclohexane,tetramethylcyclohexane and ethylcycloheptane; cyclobutene,l-methylcyclobutene, cyclopentene, 1,5-dimethylcyclohexane,l-methylcyclooctene and cyclononene; norbornane, norbornene, decaline,9-methyldecaline, cycloundene, decahydroacenaphthene,perhydrophenanthrene, perhydroanthracene and perhydrotriphenylene; andspiro- (2,2)heptane and spiro(2,4)heptane;

Aromatic hydrocarbons of 6-20 carbon atoms which may be substituted by C-C alkyl radicals, Cq-C15 aralkyl radicals of C C aryl radicals such asbenzene, toluene, Xylene, ethylbenzene, cumene, ethyltoluene,trimethylbenzene, tetramethylbenzene, hexamethylbenzene,1,2,4,S-tetraisopropylbenzene, cymene, diphenyl, diphenylmethane,diphenylethane, triphenylmethane, naphthalene, a-methylnaphthalene,fi-methylnaphthalene, 2,6-dimethylnaphthalene and1-(n-dodecyl)naphtbalene;

Acyclic or cyclic olefins of 2-20, preferably 3-18 carbon atoms havingolefinic unsaturation such as ethylene, propylene, butene-l, isobutene,butene-2, hexane-1, octene-l, 3,3-dimethylbutene-1, 4-methyl-1-pentene,nonene-l, octadecene and eicosene; vinylcyclopropane, vinylcyclopropene,vinylcyclohexane, vinylcyclohexene and 1-ethylidene-3-methylcyclohexane; and styrene, stilbene, vinylnaphthalene,triphenylstyrene, u-methylstyrene, allylbenzene and vinylanthracene;

Saturated aliphatic hydrocarbon halides of 1-20 carbon atoms such asmethyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, butylfluoride, n-butyl chloride, nbutyl bromide, n-butyl iodide, hexylfluoride, octyl bro mide, n-nonyl iodide and cetyl chloride; methylenechloride, methylene bromide, methylene iodide, fluorobromomethane,ethylidene chloride, ethylidene bromide, ethylidene iodide andpropylidene chloride; ethylene dichloride, ethylene dibromide, ethylenediiodide, propylene chloride, trimethylene bromide and octamethylenechloride; chloroform, iodoform, bromoform, carbon tetrachloride,symtetrachloroethane, pentachloroethane, hexachloroethane andhexabromoethane; and difluorodichloromethane and fluoroform;

Unsaturated aliphatic hydrocarbon halides of 2-20 carbon atoms such asvinyl chloride, vinyl bromide, allyl chloride, allyl bromide, allyliodide, isopropenyl chloride and isopropenyl iodide;1,2-dichloroethylene, 1,2-dibromoethylene, 1,2-diiod0ethylene,1,1-dichloroethylene, l,l-ditluoroethylene, trichloroethylene andtetrachloroethylene; and 2,5-dibromo 2,5-dimethylhexene-3,1,5-bromopentadecene-(l) andl4-bromo-2,fi-dimethyltetradecene-(2);

Haloderivatives of aromatic hydrocarbons of 6-16 carbon atoms such aschlorobenzene, bromobenzene, iodobenzene, fiuorobenzene, 0-, m-,p-dichlorobenzenes, o-, 111-, p-dibromobenzenes, o-, m-,p-diiodobenzenes, 1,2,4,5-tetrachlorobenzene hexachlorobenzene,pentabromobenzene, 2-fiuoro-l-chlorobenzene and 4-bromo-l-iodo-benzene;o-, m-, p-fiuorotoluenes, o-, m-, p-bromotoluenes, 2-chlorom-Xylene,l,2,4,5-tetramethyl-3-chlorobenzene and aniyl- 4-bromobenzene benzylchloride, benzylidene chloride, 1- chloronaphthalene, l-bromonaphthaleneand l-fluoronaphthalene; S-chlorotetraline, 2-bromodihydronaphthaleneand 1,2,3,4,5,S-hexachlorotetraline; l-chloro-Z-methylnaphthalene,1-chloro-2-phenylnaphthalene, l-chloro(4- chloromethyl)naphthalene,1,4-dichloronaphthalene, 2,4- dibromo l chloronaphthalene,l,3,6,7-tetrabromonaphthalene and octachloronaphthalene; and2-chloroanthracene, l-chloroanthracene, 2,3-dibromoanthracene and1,9,IO-trichloroanthracene.

Examples of the above solvent (2), (2) and (2) include the following:

As oxygen-containing organic solvents of (2), the following examples canbe mentioned.

Saturated aliphatic monoethers of 2-32 carbon atoms having an alkylradical such as dimethyl ether, diethyl ether, di-n-propyl ether,diisopropyl ether, di-n-butyl ether, diisobutyl ether, methyl ethylether, methyl n-butyl ether, n-butyl n-pentyl ether, dioctyl ether,isoamyl cetyl ether, dicetyl ether, 2,2-dibromodiethyl ether and2,2-dichlorodiethyl ether;

Aliphatic ethers of 3-20 carbon atoms having at least one unsaturatedaliphatic hydrocarbon radical such as 2- methoxybutene, methyl methacrylether, allyl ethyl ether, allyl butyl ether, 2-ethoxypropene,6-methoxy-1-hexene, ethyl vinyl ether, methyl vinyl ether,l-methoxy-Z-octene, undecenyl ethyl ether and didecenyl ether;

Aromatic ethers of 7-16 carbon atoms having a saturated alkyl or arylradical such as anisole, phenetole, isopropyl phenyl ether, tolyl methylether, diphenyl ether, ditolyl ether, dimethoxybenzene,l-ethoxynaphthalene and l-phenoxynaphthalene;

Monoethers and diethers of 7-16 carbon atoms which are halogenated andcontain at least one aromatic radical, preferably with 7 to 16 carbonatoms, such as chloroanisole, bromoanisole, 4,4-dibromophenyl ether,2,4-dichloroanisole, 3,5 dibromoanisole, 2,6 diiodonanisole,2,3,5-trichloroanisole and bromophenetole;

Saturated aliphatic monocarboxylic acid saturated alkyl esters having analiphatic monocarboxylic acid residual group of 1-21 carbon atoms and asaturated alkyl radical of 1-16 carbon atoms such as methyl formate,ethyl formate, butyl formate, ethyl acetate, n-butyl acetate, secbutylacetate, octyl acetate, butyl butyrate, methyl caproate, amyl caprylate,ethyl laurate, methyl palmitate, ethyl stearate and cetyl palmitate;

Saturated aliphatic monocarboxylic acid unsaturated alkyl esters havinga saturated aliphatic monocarboxylic acid residual group of 1-8 carbonatoms and an unsaturated alkyl radical of 2-12 carbon atoms such asvinyl acetate, allyl acetate, propenyl acetate, undecenyl acetate andhexenyl propionate;

Unsaturated aliphatic monocarboxylic acid alkyl esters having anunsaturated aliphatic monocarboxylic acid residual group of 2-12 carbonatoms and a saturated or unsaturated alkyl radical of 1-10 carbon atomssuch as methyl, acrylate, n-amyl acrylate, n-decyl acrylate, ethyl cro-6 tonate, methyl isocrotonate,meth.yl methacrylate, n-butylmethacrylate, methyl undecylenate, methyl 3-methyltetradecenate-( l3),phenyl acrylate and vinyl undccylenate;

Aromatic monocarboxylic acid saturated alkyl esters having an aromaticmonocarboxylic acid residual group of 7-18 carbon atoms and an alkylradical of l-20 carbon atoms such as methyl benzoate, ethyl benzoate,butyl benzoate, n-propyl benzoate, iso-propyl benzoate, sec-butylbenzoate, tert-butyl benzoate, n-amyl benzoate, isoamyl benzoate,neopentyl benzoate, ethyl o-, m-, p-toluylates, butyl o-, m-,p-toluylates, ethyl o-, m-, p-bromobenzoates, ethyl o-, m-,p-chlorobenzoates, ethyl 1,2-naphtl1oate and butyl 1,2-naphthoate;

Saturated aliphatic monoalcohols of 1-18 carbon atoms such as methanol,ethanol, n-propanol, isopropanol, nbutanol, isobutanol, sec-butanol,tert-butanol, l-pentanol, isoamyl alcohol, neopentyl alcohol,S-pentanol, 3- methylbutanol-Z, hexanol, octanol, lauryl alcohol,cinnamyl alcohol, phenyl ethanol, cetyl alcohol, ethoxy ethanol,2-chloropropanol, 2-bromopropanol, 3-chloropropanol, ethoxybutanol and4-chlorobutanol;

Monohydric and dihydric phenols of 6-16 carbon atoms such as phenol, o-,m-, p-cresols, thymol, o-chlorophenol, o-bromophenol, p-chlorophenol, pbromophenol, tribromophenol, catechol, resorcinol, guaiacol, eugenol,isoeugenol, o-allylphenol, 1-, 2-naphthols and anthranol;

Saturated aliphatic ketones of 3-20 carbon atoms such as acetone, methylethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyltert-butyl ketone, ethyl butyl ketone, dibutyl ketone, methyl amylketone, ethyl amyl ketone, 2-chlorobutyl ketone, ethyl 2-chlorobutylketone and Z-ethoxyethyl methyl ketone;

Saturated aliphatic diketones of 4-12 carbon atoms such asacetylacetone, diacetyl and acetonylacetone;

Aromatic monoketones of 7-18 carbon atoms such as acetophenone, ethylphenyl ketone, benzophenone, dypnone, cinnamyl methyl ketone, cinnamylethyl ketone, n-butyl phenyl ketone, tert-butyl. phenyl ketone, propylphenyl ketone, anthraquinone, anthrone, 2-acetylnaphthalene,naphthoquinone, benzoquinone and fiuorenone;

Aromatic monocarboxylic acids of 7-18 carbon atoms such as benzoic acid,o-, m-, p-toluic acids, o-, m-, p-chlorobenzoic acids, o-, m-,p-bromobenzoic acids and 1-, 2-naphthoic acids;

Saturated aliphatic monocarboxylic acids of 1-20 carbon atoms such asformic acid, acetic acid, propionic acid, valeric acid, octylic acid,undecylenic acid and stearic acid;

Saturated aliphatic carboxylic acid halides of 2-12 carbon atoms such asacetic acid chloride, propionic acid chloride and lauric acid chloride;and

Aromatic carboxylic acid halides of 7-15 carbon atoms such as benzoicacid chloride, o-, m-, p-toluic acid chlorides, o-, m-, p-chlorobenzoicacid chlorides and 1-, 2- naphthoic acid chlorides.

It has been known that when some of the above organic oxygen-containingcompounds are added as a promoter to the reaction system at the time ofpolymerization, the polymerization activity of the catalyst can beimproved by about 10-30% and the crystallinity of the obtained polymercan also be improved. However, the improvement of polymerizationactivity and the improvement of crystallinity of the obtained polymerachieved by the method of the present invention are far superior tothose attainable by the prior art.

As nitrogen-containing organic solvents of (2), the following examplescan be mentioned.

Saturated aliphatic secondary amines of 2-24 carbon atoms such asdimethylamine, diethylamine, dibutylamine and didodecylamine;

Saturated aliphatic tertiary amines of 3 to 30, preferably 3-18 carbonatoms such as trimethylamine, tributylamine and trihexylamine;

Aromatic secondary amines of 6-20 carbon atoms and aromatic tertiaryamines having 8 to 30 carbon atoms such 7 as aniline, 0-, m-,p-toluidines, xylidine, naphthylamine, N-methylaniline, N-ethylaniline,N,N-dimethylaniline, diphenylamine and triphenylamine;

Heterocyclic amines of 5-18 carbon atoms such as pyridine, 2-picoline,3-picoline, 5-ethyl-2-methyl pyridine, Z-phenyl pyridine,1,2,3,4-tetramethylpyridine, 2-chloropyridine, 2-bromopyridine,3-chloropyridine, 3-chloropyridine, 3-iodopyridine,3,4-dichloropyridine, 2,3,4-trichloropyridine,2,3,4,6-tetrachloropyridine, pentachloropyridine, 2,3-dibromopyridine,2,3,5 tribromopyridine, 2-chloro 6 methyl pyridine, 2 chlorophenylpyridine, quinoline, isoquinoline, Z-methylquinoline, 3-phenylquinoline, 6-methyl quinoline, 2,4-dimethyl quinoline,4,6-dimethyl-Z-phenyl quinoline, 3-fluoroquinoline, 4-bromoquinoline,2,6 dichloroquinoline, 5,6 diiodoquinoline, 6-bromo-2-chloroquinoline,l-methylisoquinoline, 1,3 dimethylisoquinoline, 4-bromoisoquinoline,acridine and 2-chloroacridine;

Aromatic mononitriles of 7-15 carbon atoms such as benzonitrile, o-, m-,p-tolunitriles, dimethylbenzonitrile, 4-isopropyl benzonitrile,a-naphthonitrile, fl-naphthonitrile and 9-cyanoanthracene;

Aromatic monoisocyanates of 7-11 carbon atoms such as phenyl isocyanate,toluyl isocyanate, oc-DflPhlZhYl isocyanate, fl-naphthyl isocyanate and2,4-dimethyl phenyl isocyanate; and

Aromatic azo compounds of 12-20 carbon atoms having no substituent otherthan hydrocarbon radicals or halogens such as azobenzene, o-, m-,p-azotoluenes, 1,1- azonaphthalene and 2,2'-azonaphthalene.

As silicon-containing organic solvents of (2)" (which in the presentinvention includes the cases where oxygen, nitrogen or sulphur iscontained besides silicon), the following examples can be mentioned.

Monomer type compounds (which contain one silicon atom in the molecule)represented by the general formula:

wherein Rs are alkyl or aryl radicals, Ys are substituents of variouskinds, and 11 is 1 to 4.

11:4: Tetrahydrocarbylsilanes having saturated alkyl radicals and/oraryl radicals of 4-50 carbon atoms such as tetramethylsilane,tetraethylsilane, tetrabutylsilane, tetraundecylsilane,tetra-n-octadecylsilane, ethyltrimethylsilane, trimethylpropylsilane,diethyldiphenylsilane, ethyltriphenylsilane, tetraphenylsilane, tetra(o-tolyl)silane, tetrabenzylsilane, tetra(p-diphenyl)silane and2-naphthyltriphenylsilane.

11:4: Tetrahydrocarbylsilanes having an unsaturated alkyl radical of5-28 carbon atoms such as trimethylvinylsilane;isopropenyltrimethylsilane, vinyltriphenylsilane, benzylvinylsilane andtrimethylallylsilane.

11:1 to 3, Y:hydrogen: Saturated or unsaturated alkyl or arylhydrogenosilanes of 1-30 carbon atoms having at least one SiH bond suchas methylsilane, dimethylsilane, trimethylsilane, tri-n-propylsilane,diphenylsilane, triphenylsilane, tritolylsilane and diphenylvinylsilane.

11:1 to 3, Y:halogens: Saturated or unsaturated alkyl or arylhalogenosilanes of 3-30 carbon atoms having at least one Si-halogen bondsuch as trichloromethylsilane, dichlorodimethylsilane,tripropylchlorosilane, diallyldichlorosilane, phenyltrichlorosilane,diphenyldichlorosilane, triphenylchlorosilane, tribenzylchlorosilane,triethylfluorosilane, diphenyldifiuorosilane, triethylbromosilane,diphenyldibromosilane, triethyliodosilane, chlorodifiuoromethylsilane,chloroethyldifluorosilane and dichlorofiuoromethylsilane.

12:1 to 3, Y:NH Trialkyl or triaryl silyl amines or their N-alkylaminoderivatives such as triethylsilylamine, tripropylsilylamine,triphenylsilylamine, trimethyl (N- methylamino)silane or other trialkyl(N-alkylamino)silanes and trimethyl (N,N-diethylamino)silane.

11:1 to 3, Y:alkoxy or aryloxy: Saturated alkyl or aryl silanes havingat least one Si-O-C bond such as methoxymethylsilane,dimethoxydimethylsilane, trimethoxymethylsilane, diethoxydimethylsilane,ethoxytriethylsilane, diethoxydiethylsilane, trimethylphenoxysilane andtriethylphenoxysilane.

11:1 to 3, Y:OCOR (Rzalkyl, aryl): C C aliphatic or C7-C11 aromaticmonocarboxylic acid esters of C -C trialkyl, C -C alkylaryl or C Ctriaryl silanols such as trimethylacetoxysilane, triethylacetoxysilane,triphenylacetoxysilane, trimethylbenzoyloxysilane,trimethylpropionylsilane and triethylcaproylsilane.

11:1 to 3, Y:NCO (isocyanato): Organosilicon monoisocyanates having C -Ctrialkyl, C -C dialkylaryl or C C triaryl such as trimethyl siliconisocyanate, dimethyl silicon isocyanate, tributyl silicon isocyanate andtriphenyl silicon isocyanate.

Polymer type compounds (which contain at least two silicon atoms in themolecule):

Polysilmethylenes represented by the formula (wherein x:1 to 10) such ashexamethyldisilmethylene, hexaethyldisilmethylene, hexa npropyldisilmethylene, decamethyletrasilmethylene anddodecamethylpentasilmethylene are typical, but in general theolysilmethylenes are represented by the general formula R SiCH RSiCH SiR(wherein Rs are alkyl or aryl radicals).

Linear polyalkyl or polyaryl polysilanes of 6-80 carbon atoms such ashexamethyldisilane, sym-diethyldi-npropyldiphenyldisilane,sym-diethyldi-n-propyldibenzyl disilane, hexaphenyldisilane,hexa(p-diphenyl)disilane and octaphenyltrisilane.

As derivatives thereof, alkoxy polysilanes such as 1,1,2,2-tetramethyl-1,2diethoxydisilane and pentamethylethoxydisilane.

Polyalkyl and/or polyaryl cyclopolysilanes of 12-120 carbon atoms suchas dodecamethylcyclohexasilane and octaphenylcyclotetrasilane.

Dialkylpolysilanes, alkylarylpolysilanes and diarylpolysilanes which arelinear molecules represented by the general formula:

wherein R, R, R" are the same or different, represent alkyl radical of1-4 carbon atoms, aryl radical of 6-8 carbon atoms or hydrogen, and xstands for an integer of 1-1000, such as hexamethyldisiloxane,decamethyltetrasiloxane, tetracosmethylundecasiloxane,3-hydroheptamethyltrisiloxane, 3,5-dihydroctamethyltetrasiloxane,3,5,7-trihydrononamethylpentasiloxane,tetramethyl-1,3-diphenyldisiloxane, pentamethyl-1,3,5triphenyltrisiloxane, hexaphenyldisiloxane and octaphenyltrisiloxane.

As compounds obtained by halogenating both ends of the molecule of theabove compounds, u,w-dihaloalkylpolysiloxanes represented by the generalformula:

wherein X is a hologen atom and x:1 to 1000, such as1,3-dichlorotetramethyldisiloxane, 1,5-dichlorohexamethyltrisiloxane and1,7-dichlorooctamethyltetrasiloxane are representative.

Alkylcyclopolysiloxanes represented by the general formula:

(R"'HSiO) wherein R is an alkyl radical of 1-4 carbon atoms, y standsfor an integer of 3 t0 8, such as 2,4,6-trimethylcyclotris'iloxane and2,4,6,8 tetramethylcyclotetrasiloxane.

Alkylcyclopolysiloxanes represented by the general formula:

(R!I|I2'SiO)z 'wherein R"" is an alkyl radical of l-4 carbon atoms, zstands for an integer of 3 to 9, such as hexamethylcyclo- 9 trisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane anddodecamethylcyclohexasiloxane.

Arylcyclopolysiloxanes represented by the general formula:

wherein Q is an aryl radical of 6-8 carbon atoms and 1 stands for aninteger of 3 to 6, such as 1,3,5-triphenyl- 1,3,5trimethylcyclotrisiloxane, hexaphenylcyclotrisiloxane andoctaphenylcyclotetrasiloxane.

Alkyl or aryl polysilazanes having 6-50 carbon atoms and a molecularweight not more than 1000 such as hexamethylsilazane,hexamethyltrisilazane, N-methylhexamethylsilazane,octamethylcyclotetrasilazane, hexaphenyl cyclotrisilazane,hexaethylcyclotrisilazane, hexaphenylcyclotrisilazane,hexa(n-butyl)cyclotrisilazane and hexaphenylcyclotrisilazane.

In the present invention, any methods of pulverizing titaniumtrichloride obtained by reduction of titanium tetrachloride withmetallic aluminum can be used which are capable of pulverizing thetitanium trichloride composition until the ozor -type of the X-raydiffraction pattern of the crystal of titanium trichloride cannot beidentified. For example, such physical or mechanical pulverizing meansas ball mill pulverization, vibratory mill pulverization and impact millpulverization may be cited. The pulverizing step is carried out in theabsence of the auxiliary component.

The pulverization may be carried out at room temperature, but ifdesired, it may be performed at lower or higher temperatures, forinstance, -20 C. to +100 C. The pulverization can be performed in anatmosphere of an inert gas such as nitrogen gas, and if desired, otherinert gas such as argon and helium.

The amount of the solvent mixture and the ratio of the inert organicsolvent to the other solvent (2), (2) or (2)" are optional, butgenerally, the amount of the solvent mixture is 1 to 100 parts by weightper part of the pulverized titanium trichloride composition. The othersolvent (2), (2) or (2)" may be used in an amount of 0.005 to 10.0 partsby weight per part of the titanium trichloride composition.

In the case of using the mixed solvent containing the organicoxygen-containing compound (2) mentioned above, the amount of theoxygen-containing compound is 0.005 to 10.0 parts by weight per part ofthe titanium trichloride composition, preferably 0.01 to 10.0 parts forothers, 0.01 to 5.0 parts for ketones and esters, 0.005 to 0.3 part foralcohols, 0.005 to 0.2 part for phenols and aldehydes, and 0.005 to 0.5part for carboxylic acid halides and carboxylic acids.

In the case of the mixed solvent containing the organicnitrogen-containing compound (2), the amount of the organicnitrogen-containing compound is usually 0.005 to 0.5 part by weight perpart of the titanium trichloride composition, preferably 0.01 to 0.5part by mole for heterocyclic amines (nitrogen-containing heterocycliccompound) and aromatic tertiary amines, 0.01 to 0.3 mol part fortertiary amines, isocyanates, azo compounds and nitriles, and 0.005 to0.2 mol part for secondary amines.

In the case of the mixed solvent containing the organicsilicon-containing compounds, there is no particular limitation on theratio of the amount of such compound to that of the titanium trichloridecomposition. However, the preferred range of the amount per part byweight of the titanium trichloride composition is 0.05 to 10 parts byweight for organohalogenosilanes, 0.05 to 5.0 parts by weight fororganoalkoxy silanes, aryloxy silanes and organopolysiloxanes, 0.02 to2.0 parts by weight for organosilanol carboxylic acid esters andorganosilazanes, and 0.02 to 1.0 part by weight for the organisocyanatesilanes (alternatively called organosilicon isocyanate). The preferredamount of organosilanols is 0.02 to 1.0

part by weight, and that of organosilthianes is 0.02 to 2.0 parts byweight.

When preparing a mixed solvent comprising various compounds selectedfrom (1), (2), (2) and (2)" mentioned above, these compounds should bemixed at the ratios described above. The ratio of an amount of the inertorganic solvent 1) to the other solvent 2), (2) and (2) may be varied atany desired ratios, but generally, the amount of the inert solvent islarger.

There is not any particular restriction on the extraction of thepulverized titanium trichloride composition with the mixed solvent. Itmay be contacted with the mixed solvent at room temperature, or atelevated temperatures with stirring, or under cooling. Generally, thecontacting may be performed at from 60 to 0, usually at 20100 C. forseveral minutes to several days. At this time, it is desirable toperform the separation of the mixed solvent from the titaniumtrichloride composition as sufiiciently as possible. For this purpose,it is preferable to wash or extract and wash the separated compositionfurther with a pure inert organic solvent 1). Such a Washing operationcan be carried out a plurality of times.

Such treatment may be effected by a batchwise washing method, orextraction with a Soxhlet extractor, or by a continuous countercurrentwashing. By any of these methods, the mixed solvent used should beseparated from the treated titanium trichloride composition as far aspossible.

The extracted and separated titanium trichloride composition thusobtained may be stored in an oxygen-free and water-free condition in theform of slurry in an inert organic solvent (1) or in the form of driedpowder. The drying step can be carried out at a temperature as low aspossible under the same conditions as described above.

The catalyst used in the present invention consists of an organoaluminumcompound and the titanium trichloride composition obtained by theaforementioned procedure. Any organoaluminum compounds can be used whichare known as one component of the Ziegler-Natta type catalyst.

Examples of such organoaluminum compounds include, for instance,trialkylaluminum, dialkylaluminum halides, dialkylaluminum alkoxides,alkylaluminum alkoxy halides, alkylaluminum dihalides, reaction productsof these with electron-donor compounds, or reaction products of thesewith alkali metal halides or alkali metal complex fluorides oftransition metals. Examples of the electrondonor compounds aredescribed, for example, in US. Pats. Nos. 3,081,287, 2,116,274 and3,230,208.

The OL-OlCfil'l monomers to be polymerized with the catalyst of theinvention are, for instance, propylene, l-butene, 4-methyl-1-pentene,styrene, l-pentene, 3-methyl-l-butene, and trimethyl vinyl silane. Thecatalyst can also be applied to the copolymerization of ethylene withpropylene, ethylene with l-butene, ethylene with l-hexene, or propylenewith styrene, and also to the homopolymerization of ethylene.

The polymerization of a-olefins using the catalyst of the invention maybe performed b any known means under known conditions. For instance, thepolymerization can be performed at a temperature of 20 to 100 C. and apressure of normal atmospheric pressure to 100 kg./ cm. Thepolymerization may be conducted in an inert solvent or in the absence ofa solvent where the liquefied monomer acts as a solvent in some caseseither batchwise or continuously.

In the polymerization of olefins. according to the process of theinvention, hydrogen may be used as a molecular weight regulating agentfor olefin polymers. After completion of the polymerization, thecatalyst is generally deactivated with lower alcohols such as methanol,ethanol, butanol, and isopropanol in the same way as the Ziegler- Nattatype polymerization of olefins. But where the yield of polymer per unitamount of the catalyst is large, the aforementioned deactivatingtreatment may be omitted,

and the catalyst may merely be contacted with air or water vapor.

The invention will further be described by the following examples andcomparative Examples which are not intended to limit the invention inany way.

EXAMPLES 1 TO 2, CONTROL AND COMPARA- TIVE EXAMPLES 1 TO 6 Preparationof metallic aluminum-reduced titanium trichloride Titanium tetrachloride(4 liters) was reacted with 54.0 g. of metallic aluminum powders in thepresence of 3.0 g. of aluminum chloride in a stainless steel autoclaveat the boiling point of titanium tetrachloride for 20 hours. Unreactedtitanium tetrachloride and free aluminum chloride were removed bydistillation at atmospheric pressure from the titanium trichloridecomposition which was obtained. The remaining solid was heated for hoursat 200 C. at a reduced pressure of 0.2 mm. Hg to remove the remainingtitanium tetrachloride. As a result 1153 g. of a light reddish purpletitanium trichloride composition (to be abbreviated as TiCl Ahereinafter) were obtained.

Activation of TiCl 120 grams of this titanium trichloride compositionwere put into a cylindrical stainless steel vessel having an innercapacity of 800 ml., and milled at 140 rpm. for about 24 hours in anatmosphere of nitrogen in the presence of 850 stainless steel balls eachhaving a diameter of mm. until the 04-, y-type of the X-ray diffractionpattern of the titanium trichloride component could not be identified.

The particle size adjustment of the pulverized component for the removalof fine particles having up to 40 in diameter was carried out in anatmosphere of nitrogen.

Extraction The pulverized composition was extracted for 2 hours at 70 C.with the solvent consisting of 5 molar parts of toluene and 0.5 molarpart of anisole per molar part of the composition indicated in Table Iausing a Soxhlet extractor equipped with a glass filter to form atitanium trichloride composition to be used as a component of thecatalyst.

Polymerization of propylene A l-liter glass separable four-necked flaskequipped with a stirrer, a thermometer, a propylene inlet and an exhaustpipe was charged with 500 ml. of refined kerosene, and purged withnitrogen with substantial stirring. The titanium trichloride component(2.00 g.) obtained above and 10 millimols of diethylaluminum chlorideand the temperature was decreased. Methanol (100 ml.) was added todeactivate the catalyst. The polymer slurry was filtered, and thepowdery solid obtained on a filter plate was washed several times withmethanol, and dried for 2 days at 70 C. under a reduced pressure of mm.Hg to yield a solid propylene polymer. The results obtained are shown inTable I-a. This table also shows the results obtained in the control inwhich propylene was polymerized in the same manner as in Example 1except using the titanium trichloride composition not pulverized;Comparative Example 1 in which propylene was polymerized in the same wayas set forth in Example 1 except that the extracting treatment of thetitanium trichloride composition was omitted; comparatively Example 2 inwhich the procedure of Example 1 was repeated except that the titaniumtrichloride composition used in control was extracted and washed in thesame way as in Example 1, and the resulting titanium trichloridecomposition was used; Comparative Example 3 in which the procedure ofExample 1 was repeated except that a titanium trichloride compositionwas first extracted and washed with a solvent and then pulverized;Comparative Example 4 in which the procedure of Example 1 was repeatedexcept that a titanium trichloride composition obtained by extractingthe titanium trichloride composition used in Comparative Example 3further with two solvents one by one was used; Comparative Example 5 inwhich the procedure of Example 1 was repeated except that a titaniumtrichloride composition obtained by reducing titanium tetrachloride withmetallic aluminum in the presence of anisole and without pul verizing,extracted with a solvent in the same manner as set forth in Example 1was used; and Comparative Example 6 in which the procedure of Example 1was repeated except that a titanium trichloride composition used wasobtained by reducing titanium tetrachloride with hydrogen.

In all of the tables appearing in this specification, T.I. stands fortotal isotacticity which expresses the percentage of the weight ofpolymer difficulty soluble in a specific extracting solvent (usuallyheptane) based on the weight of total polymer formed (a portion of thepolymer readily soluble in a polymerization solvent is weighed afterevaporation of the solvent, and included in the weight of the totalpolymer). On the other hand, partial isotacticity indicates thepercentage of the weight of a polymer insoluble in a specific extractingsolvent based on the weight of polymer excluding the weight of a portionreadily soluble in a polymerization solvent. Usually, therefore, thetotal isotacticity is smaller than the partial isotacticity, AD. is anabbreviation of apparent density; the weight of the polymer is expressedin grams and its apparent volume, in cubic'centimeters.

TABLE I-a TlCla component Milling treat- Polypropylene ment Extractiontreatment step step, Organo- Total yes Yes aluminum yield T.I. Reductionor no or no Solvent compound (g.) (percent) Example 1 Al Yes. Yes.Toluene plus anisole (CzHQzAlCl 153.2 96.0 Example 2* Al 0 Yes ..d0(CzH5)zAlCl 171.2 95.7 Control Al No 0 (C2H5)2A1C1 6.5 93.3 Comparative1 AL. Yes..." 0 (CzH5)2A1Cl 71.0 88.8 Comparative 2.- AL. N0 Yes...Toluene plus ansole (CzH5)2A1C1 6. 7 92. 9 Comparative 3-. AL. Yes.-."Yes..- Tolufine plus anisole (extracted before (C2H5)2A1C1 62.3 86. 9

ml mg Comparative 4.. Al Yes"... Yes... 1st anisole, 2nd toluene(extracted (C2H5):A1C1 53.2 93.1

with two solvents one by one). Comparative 5.- Al plus (toluene/anisole)N0 Yes.-. Toluene plus anisole (C2H5)2A1C1 10.3 94.0 Comparative 6Hydrogen Yes Yes ..do (C2H )2AlC1 66.2 86.3

*TiChAA manufactured by Stauffer Chemical Co. was used.

"T1013 was prepared in the presence of 6 ml. of toluene by reacting 1mol of TiCh, 10.8 ml. of anisole and 0.1 mol of Al powder for 12 ltrs.,then filtering, washing with toluene three times and dried.

were added in this order in an atmosphere of nitrogen, and thetemperature was raised to C. Thereafter, propylene was introduced andpolymerized for 2 hours at atmospheric pressure. After completion of thepolym erization, the propylene was replaced by nitrogen gas,

EXAMPLES 3 TO 35 AND COMPARATIVE EXAMPLES 7 TO 10 The polymerization ofpropylene was performed in the same way as set forth in Example 2 usingeither the of the titanium trichloride composition having fineparticles. The results obtained are given in Table I-b. I

TABLE I-b of the same titanium trichloride component as used in Example2 was mounted in a thermometer fitting pipe in the autoclave so thatupon rotation of a stirrer, the stirring vanes would collide with theampoule and break it. The inside of the autoclave was further purgedwith propylene gas, and 600 g. of propylene and 7.5 millimols ofdiethylaluminum chloride were introduced into the autoclave at roomtemperature, followed by introduction of 2200 ml. of hydrogen. Thesystem was heated to 50 C.,

10 and then the stirrer was operated. On breakage of the ampoule, thepolymerization of propylene was started. After polymerizing for 4 hours,unreacted propylene was 'IiClx component Polypropylene Extractionsolvents Total 'I.I.

Class Amount 1 0. Hours l fi Example 3 .-{ggggfi fifig 29 125.7 95. 7 0.365 Exam le 4 2 206. 5 94. 6 0. 377 Exam le 5 niggi ggga- 28 92.6 95.0330 Example 6.- {gfifif 3x24 145. s 95. 3 0.346 Example 7...- lfig g g2 93. 94.6 0. 351 Example 5 .ig g ggq 23 115. 3 95.3 0. 379 E am le 9figi ;fifi& 22 132.3 94.9 0.366 Example 10 aggggg }r.t 12 129. 0 95. 10. 352 Exam le 11 1 2 }70 2. 0 323. 1 96. 3 Comparative 7 2 163 90.1Exam le 12 agg ggg g }70 2. 0 215 39. 3 Exam le 13 ..{'g }r.t 19-20 95.0 95. 9 0. 339 Example 14 ngfigfl gg 0' }1.1 19-20 102.1 94. 3 0. 333Exam le 15 --{gg g jg: he 86.8 95. 5 0. 319

I Exam le 16 ngggyg 0 }r.t 24-25 93. 3 95. 4 0. 345 Exam le 17 g g }r.t.19-20 75. 0 94.3 0. 355 Exam le 13 ..{gg gg 0' }x.t 5x25 97 1 93.6 0.375Exam le 19 Q }r.t.- 5x24 100.9 94.7 0.349 Example 20 }r.t. 5x24 100. 595. 6 0.357 Example 21 .igf t jgj 0. ,1.1. 6x24 73. 0 94.0 0. 355 Examle 22 f- O }r.t. 6x24 74. 2 94.1 0. 331 Example 23 aggiggg g }r.t. 2x2476.8 94.0 0.350 Example 24 aflfigtgi eg }r.t. 2x24 73. 4 94.2 0.376Example 25 agggggg }r.t. 2x24 75. 4 94.7 0. 359 Exam le 26 ..{'g g }702. 0 147. 7 94. 3 0. s Comparative 8. 53. 2 87. 2 Example 27 }00 2 0 7s.3 94. s 0. 362 Example 23 g 2 o 33.3 95.4 0.351 Example 29 g }60 2 090.1 94.9 0. 349 Example 30 Anisole }60 2 o 75. 2 95. 6 0.371 Example 31"$325331 2 }60 2. 0 142. 3 95. s 0. 367 Exam le 32 aggfggge }60 2.0 125.9 96.1 0.355 Exam le 33 4 2 2 0 199 6 96.3 0. 397 4 Exam le 34 4 g }702. 0 s9. 2 85.8 0. 286 Comparative 9 4 50. 2 81. 9 0. 251 Exam le 35 }702 0 26 91.3 Comparative 10 15 85. 6

, The amount stands for a molar part of each extraction solvent added to1 molar part of the titanium trichloride composition.

1 The procedure will be described below in the description of Example 11and Comparative Example 7.-

3 The procedure of Example 11 was repeated except that 0.014 g. of theextraetedtitanium trichlorlde composition was used and thepolymerization Was carried out at a temperature of 80 C. for 8 hours.

5 The procedures employed will be described in the Example 33, Example34 and Comparative Exam- .ple9, Example 35 and Comparative Example 10,respectively.

EXAMPLE 11 AND COMPARATIVE EXAMPLE 7 The inside of a 2-liter autoclavewas sufiiciently purged flushed, and the catalyst was deactivated withthe addition of methanol. Polypropylene was obtained in an amount of383.1 g. It had a crystallinity of 96.3% and an with a nitrogen gas. Aglass ampoule containing 0.2 g. of 2.55.

When the foregoing procedure was repeated except that TiCl (AA)mentioned above was used as a titanium trichloride composition notextracted and washed with toluene, polypropylene was obtained in anamount of 163 g. It had an [1 of 2.82 and a crystallinity of 90.1%

16 and 70 ml. of 4-methyl-l-pentene were added dropwise over a period of10 minutes. The polymerization was performed for one hour, and theproduct was post-treated in the same way as set forth in Example 2. Theyield of the polymer produced was 26 g., and it had a crystallinity of(Comparative Example 7). 91.3%.

EXAMPLE 33 when the foregoing procedure was repeated except that atitanium trichloride composition not extracted A l-hter separablefour-necked flask equipped with a inlet for insertion of a thermometer,a nitrogen inlet, and (TlclBAA) an exhaust outlet was charged with 3.0liters 0t refined and washed with toluene was used, the polymer wasobkerosene and 120 g. of potassium t1tan1um fluoride, and tained in anamount of g., and it had a crystallinity with stirring, the inside ofthe flask was sufiiciently purged of 85.6% (Comparative Example 10).with nitrogen. Ethylaluminum dichloride (254 g.) was then added, andthese components were reacted for- 6 15 hours at 60 C. The product wascooled to room temperature, and allowed to stand. The supernatant liquidwas re- Extraction covered. The concentration of organoaluminum com- 200g. of the pulverized t1tan1um trichloride composig g ig ifi gf alummum mthe supernatant hquld was tion (TiCl AA) obtained in Example 2 wereextracted A Miter e arable fourmecked flask ui ed ith a at 50 C. for 4hours in l-liter glass flask equipped with stirrer a .nlet the m t equst a stirrer, thermometer, dropping funnel and nitrogen gas i e f g b;1 r ig g i ig zg i inlet and outlet line, with a solvent mixtureconsisting of P as W m o 500 ml. of toluene and 0.12 mole of a-picolineWhile stirring, the inside of the flask was fully purged with m-Stirring gs 2 3?: iz of the fi gg s z Separation of the titaniumtrichloride composition gg E i c :3 g i Y i g from the solvent mixtureby means of a glass filter plate u Seque f 1 ndrthe was carried out.Then, the composition was washed with f zg 5 t 32 6 X l g hi refinedtoluene three times to remove the residual sol- T er a g d z g i a of t1 01 to fi vent mixture in the composition as completely as possible. pyene a P05 r r 1 gp yp py The drying under vacuum gave improved titaniumtriwere carried out as in Example 2. The yield of the SOlld chloride comositions polymer (polypropylene) was 199.6 g., and it had a bulk papparent density of 0.387 and a crystallinity of 96.3%. Polymerizationof propylene EXAMPLE 34 AND COMPARATIVE EXAMPLE 9 A l-liter glasspolymerization vessel equipped with a 35 stirrer, a thermometer, apropylene gas-inlet and an ex- The Polymenzatlon of PIEJPYIeHe wasPfirformed the haust line was fed with 500 ml. of refined kerosene andm? manner as Set fQrth m Example @fcePt that P the system wassubstantially purged with nitrogen. Ten millimols of ethylalummumethoxychloride instead of d1- millimoles (199 g.) of the titaniumtrichloride composi qthylalummum chlonde were used and t Polymmw tionobtained above and 10 millimoles of diethylalumiwas Performed hours-Yield of Polypro 4:0 num chloride were added to the system which wasthen pylene was go and It had a crystanlmty of 858% and heated to atemperature of C. The polymerization was a bulk denslty of performed at70 C. for 2 hours at an atmospheric pres- When the foregomg f f repeated exceptfllat sure while introducing propylene. After completion ofthe T161 (AA) was used as a titanium trichloride compositionPolymerization, the catalyst was decomposed with meth not extracted withtoluene ,the amount of total polypro- 45 anol followed by Separation ofSolid polymer from the pylene yielded was 50.2 g., and it had a crystally of liquid phase by filtration. The solid polymer was dried 819% and abulk denslty of '2 (Comparatlve Exam at C. under reduced pressure. Thekerosene layer of P18 polymer solution was concentrated to determine theamount of polymer dissolved in kerosene. The total yield EXAMPLE 35 ANDCOMPARATIVE EXAMPLE 10 50 of polymer was the sum of the amounts of thepolymers Using the apparatus used in Example 2, 2.00 g. of the both inthe solid and dissolved forms. same titanium trichloride composition asused in Example The results of polymerization obtained using each of 2,and 20 millimols of diethylaluminum chloride were titanium trichloridecompositions and hydrogen-reduced added. With stirring, the mixture washeated to 40 C., titanium trichloride were as shown in Table II-a.

TABLE II-a TlCla component Milling treatment step Auxiliary componentPolypropylene Extraction treatment step Amount Organo- Total T.I. YesYes aluminum yield (per- A.D. Reduction or no Class M1. M01 or noSolvent compound (g.) cent) (g./ce.)

Example 36.- Al Y Yes.-- Toluene plus (C2H5)2A1Ol 152.5 95.1 0. 379

a-picoline. Control Al No N (GzHQzAlCl 6.5 93.3 0.369 Comparative 11-A1"... Y N (CzH5)zA1Cl 63.2 93.2 0.377 Comparative 12. Al N Yes..-Toluenelplus (C2H5)zAlCl 6.7 92.9 0.353

' 1118. Comparative 13. Al Yes Yes... T li l ene plus (CzH5)2AlC1 63.889.6

no (extracted before milling). Comparative 14. A1 Yes Yes... 1sta-picoline, 2nd (CzHmAlCl 6. 0 89.7

toluene (extracted with two solvents one by one). Comparative 15 Al plustoluene plus No Yes-.. Toluene plus (C2H5)zAlCl 52.0 88.8 a-picoline.a-picoline. Comparative 16- Hydrogen Yes..- 1.5 0.015 Yes do (CzHQzAlCl64.4 90.1

1 TQiuene/a-picoline.

In a 500 ml. glass flask equipped with a stirrer, a thermometer, adropping funnel and nitrogen gas inlet and outlet line were placed asolvent mixture consisting of 300 ml. of toluene and anitrogen-containing compound the amount and class of which are indicatedin Table II-b. Extraction was carried out at a temperature for a periodindicated in such table. Separation of the titanium trichloridecomposition from the solvent mixture was carried out by means of a glassfilter plate followed by washing the composition with refined tolueneseveral times and successively drying under reduced pressure at roomtemperature.

Polymerizations were performed using the resultant titanium trichloridecompositions in the same manner as in Example 36. The results were asillustrated in Table IIb.

When the foregoing procedure is repeated except that a titaniumtrichloride composition not extracted and washed with toluene was used,polypropylene was obtained in an amount of 84 g. It had a bulk densityof 0.279 and a crystallinity of 82.5% Ccomparative Example 18).

EXAMPLE 51 AND COMPARATIVE EXAMPIJE 19 and the polymerization wasperformed for two hours. The yield of total polypropylehewas 135.8 g.,and it had a crystallinityof 86. 3

When the foregoing, procedure was repeated except that a titaniumtrichloride composition not extracted with toluene was'used, the amountof total polypropylene 7 TABLE 11-3 7 p h TiCla component olybmpyleneExtraction solvents Total v Q 7 T.I.

' yield (per- A.D. Class Amount 0. Hours (g.) cent) (g./ce.).

Example 37- {ffil gfli j }50 44 152. 5 95. 1 0. 379 Example ssflulggfigg I he"... 48 133.5 96.1 0. 378 Example 39.-

lgj gfi 48 151. 2' 9.5. 0. 362 Example 40. 48 120.1 94. 4 0. 366 Example41 gffggg }r.t 4s 112.3 93.0 0.371 Example e2.-...{$; 48 120. s 94. 0.302 Example 43-...-{

}s0.- 2 133. 1 04. 7 0. 372 Example 0 2 141.3 N 95.3 0.365 Example45..-.-{ }s0. 2 121.7 95.0 0.360 Example 46. }e0 2 99. 2 e5. 7 .331Example 4.7-

39% }e0. 2 90. 3 95. 3 o. 354 Example 43-...-{ }e0 2 108.0 04.2 0.361Example 49-.-.-{Effifi }s0 2 89.3 94.4 0.351 Comparative 17.{gjgFgi Ei9? }60 2 42. 8 92. 8 0. 341 =---littttiae::::::::::::::::: e 93 4 1580-340 Clinparative I I V 84 W Example lil ltilfseiiii:::::::::::::::::::efl 4 135-8 Ctignparative i H .1... 82.1 m=----{3%lt2lfee1i3:::f:::::::::iIiIQQ (fig 1 ,2

1 The amount is indicated in milliliters in the'case of toluene; inmolar ratio per mole of TiClx in the case of the nitrogen-containingcompound.

1 The procedures were shown in the following descriptions of ExamplExample 51 and Comparative Example 19 and Example 52 respectively.EXAMPLE 50 AND COMPARATIVE EXAMPLE 18 e 50 and Comparative Example 18,

= yielded we'e'sspe g., and it had a crystallinity of 32.1%

The inside of a 2-liter autoclave was sufliciently purged with anitrogen gas. A glass ampoule containing 0.017 g.

the stirring vanes would collide With the ampoule r (Comparative Example19).

' 1 7 EXAMPLE 52 Using theapparatus used in Example 36, 2.0 g. of thesame titanium trichloride composition as used in Example,36,- andmillimols of diethylaluminum chloride and break it. The inside of theautoclave was further" purged with propylene gas, and 460 g. ofpropylene'and. 7.5 millimols of diethylaluminum chloride were introducedinto the autoclave at room temperature, followed,

by introduction of 2200 ml. of hydrogen. The sytem was was started.After polymerizing for 8 hours, unreacted propylene was flushed, and thecatalyst was deactivated with the addition of methanol. Polypropylenewas ob-"u tained in an amount of 158 g. It had a bulk density off-g0.340, a crystallinity of 87.8% and an [17] of 3.58....

were added. With stirring, the mixture was heated to C., and ml. of4-methyl-l-pentene were added dropwise over a period of 10 minutes. Thepolymerization was performed for one hour, and the product waspost-treated in the same way as set forth in Example 36. The yield ofthe polymer produced was 29 g., and it had a crystallinity of E AMPLE 53ANDYVCOMPARATIVE EXAMPLES r I Activation A 800 ml. stainless steelcylindrical vessel was charged .with g. of an unpulverized titaniumtrichloride comhaving a diameter of 10 mm.

Extraction 200 g. of the pulverized composition obtained were extractedwith a mixed solvent consisting of 500 ml. of toluposition.

Polymerization ride composition was recovered by filtration from themixed solvent, and washed three times with pure toluene to remove theremaining mixed solvent, followed by drying in vacuo to form a modifiedtitanium trichloride com- Polymerization of propylene was performedusing the ene and 20 ml. of polymethylsiloxanes having a viscosity TableIII-a.

modified titanium trichloride composition in the same manner as setforth in Example 1. The results are shown in TABLE III-a TiCla componentMilling treatment step Extraction treatment Polypropylene Auxiliarycomponent step Organo- Total T.I. Yes Amount, Yes aluminum yield (per-A.D. Reductlon or no Class ml. or no Solvent compound (g.) cent)(g./cc.)

Example 53 Al Yes.-. Toluene/poly- (CzH)zAl 118. 3 94.1 0. 369

methyl siloxane Contro1 A1 No. (C2H5)ZAI 6. 0 93. 3 0. 369 Comparat ve20. Al N0. (C2H5)2Al 63. 2 93. 2 0. 377 Comparative 21- Al o Yes-(C7H5)2Al 6. 7 92. 9 0.353

methyl siloxane. Comparative 22. A1 Yes- Yes-.. Toluene/poly- (CgH5)zAl68. 9 88.0

methyl siloxane (extracted before milling). Comparative 23. Al Yes.....2- Yes-.. Toluene (C H5)2Al 71. 5 93. 5 0.366 Comparative 24- Al plustoluene No Yes"- Toluene/poly- (CzHQzAl 73. 5 87.0

polymethyl methyl siloxane. siloxane. Comparative 25. Hydrogen Yes..-Toluene/poly- 1. 5 Yes do (CZHQZAI 67. 4 89. 2 0.341

methyl siloxane.

of centistokes represented by the general formula tel.

at 70 C. for 2 hours with stirring. The titanium trichlo- Table IIIb.

EXAMPLES 54 TO 77 AND COMPARATIVE EXAMPLES 26 TO 28 TABLE III-bPolypropylene T1013 component Total T.I.

yield (per- A.D.

Class Amount (g.) cent) (g./ec.)

Example --{%Z1Z,Eii1}gax;;a; ":3; igfain n 141-2 0-362 Example--{%ffifiraxsuaa igfgfin 101-3 1 @7344 Example 56--{$$i%i%?i3;asn;aanaa:: ":3: 239.3%: 2 9e 0 344 Examples?--{%iii3fi3i;seina i fa fiiniiii 0-399 Example 58 gfi ffilttyisfiiaiaaai'." ifii'ill} 0-371 522232313511;Fiiiiiii iggmlm-i} 11?. 33.231323 Comparative 27..-{ ;g%L 6. 7 92. 9 0. 353 Example 60 ..{g %fff-12s. 0 94. a o. 377 Example 61 5? 140. o 93. 7 0. 379 Example 62 ggfggggge 90. 2 9s. a 0. 331 Example ea ggg gfgi gfi: 100 121.5 95. a 0.362Example h fiitfiaanagramrants. 130-3 Example h gl i e hfl silicontsoeyanate 1 4 325 Examplefifiiiiit ry"lsnrn'ianaratime- 1452 0-354Example 67. g gf f figfl gg wg 103. 3 93-9 0. 349 Example$333531;tinaeaa'znrianaazareas;weat): QB ETII} 124 89 0-3552332:2212;:litterW ?eeernerea gm: 2;; 2:12

TABLE III-bContinued Polypropylene TiCl; component Total 1.I.

yield (per- A.D. Class Amount (g.) cent) (g./cc.)

Toluene 500 ml. Example 70 a "illgolymethyl siloxane (kinematicviscosity 2O cs 3 enzene Example 71 p 01y (mane 95. z o. 377

erosene Example 72 gimethyl polysfloxanenu 94. 8 0. 369

exane Example 73 polysnoxaneun 93.8 o. 354 Example 74 94. 1 0. 345

Example 75 He 94. 9 0. see

Tn'chloroethylene- Example 76 nhg g l qgzi 300 9a. 9 0. 344

ar on 'su e ml. Example 77 {Dimethyl polysiloxane 6 ml 9 7 369 1Polymerization of propylene was performed in the same way as set forthin Example 50 except that the titanium trichloride composition as usedin Example 53 was employed in an amount of 0.015

'- Polymerization of propylene was performed in the same way as setforth in Example 51. 8 Polymerization of e-methyl-Lpentene was performedin the same way as in Example 52.

The silicone oil (1) in Example 60 has the following structural units:

fi O Zi O v \L 'le' lm \J)COMe/u Me: CH group K. vis.= cs.

The silicone oil (2) in Example 61 has the following structural units:

K. vis.=55 cs.

The structural units of the silicone oil (3) used in Example 62 are asfollows:

iiiollliu \le \lH/, V y

Me: CH group j K. vis.=32 cs.

What we claim is:

1. In a process for polymerizing or copolymerizing a monomer selectedfrom the group consisting 'of ethylene, propylene, l-butene,4-methyl-l-pentene, styrene, l-pentene, l-hexene and S-methyl-l-butenein the presence of a catalyst composed of a pulverized titaniumtrichloride component and an organo-aluminum compound, the improvementwherein said monomer is polymerized or copolymerized in the presence ofa catalyst comprising:

(A) a titanium trichloride composition obtained by pulverizing acomponent consisting of an aluminumcontaining titaniumtrichloridecomponent prepared by the reduction of titanium tetrachloridewith metalhe aluminum, until the aor -type crystal structure of saidtitanium trichloride cannot be identified in the X-ray diffractionpattern, and extracting the re sulting titanium trichloride compositionwith a solvent mixture of an inert organic solvent? 7 5 (1) selectedfrom the group consisting of aromatic hydrocarbons having 6 to 20 carbonatoms, saturated aliphatic hydrocarbons having 3 to 20 carbon atoms,alicyclic hydrocarbons having 3 to 18 carbon atoms, acyclic or cyclicolefins of 2 to 20 carbon atoms, unsaturated aliphatic hydrocarbonhalides of 2 to 20 carbon atoms, saturated aliphatic hydrocarbon halidesof 1 to 20 carbon atoms, halogenated aromatic hydrocarbons having 6 to16 carbon atoms and carbon disulfide; and a member selected from thegroup consisting of the following organic solvents;

(2) an oxygen-containing organic solvent selected from the groupconsisting of saturated aliphatic monoethers having 2 to 32 carbon atomshaving an alkyl radical, aliphatic ethers of 3 to 20 carbon atoms havingat least one unsaturated aliphatic hydrocarbon radical, aromatic ethersof 7 to 16 carbon atoms having a saturated alkyl or aryl radical,monoethers and diethers of 7 to 16 carbon atoms which are halogenatedand contain at least one aromatic radical, saturated alkyl esters ofsaturated aliphatic monocarboxylic acids having an aliphaticmonocarboxylic acid residual group with 1 to 21 carbon atoms and asaturated alkyl group with 1 to 16 carbon atoms, unsaturated alkylesters of saturated aliphatic monocarboxylic acids having a saturatedaliphatic monocarboxylic acid residual group with 1 to 8 carbon atomsand an unsaturated alkyl group with 2 to 12 carbon atoms, alkyl estersof unsaturated aliphatic monocarboxylic acids having an unsaturatedaliphatic monocarboxylic acid residual group with 2 to 12 carbon atomsand a saturated or unsaturated alkyl group with 1 to 10 carbon atoms,saturated alkyl esters of aromatic monocarboxylic acids having anaromatic monocarboxylic acid residual group with 7 to 18 carbon atomsand a saturated alkyl group with 1 to 20 carbon atoms, saturatedaliphatic monoalcohols having 1 to 18 carbon atoms, monohydric anddihydric phenols having 6 to 16 carbon atoms, saturated aliphaticmonoketones having 3 to 20 carbon atoms, sat urated aliphatic diketoneshaving 4 to 12 carbon atoms, aromatic monoketones having 7 to 18 carbonatoms, aromatic monocarboxylic acids having 7 to 18 carbon atoms,saturated aliphatic monocarboxylic acids having 1 to 20 carbon atoms,saturated aliphatic carboxylic acid halides having 2 to 12 carbon atomsand aromatic carboxylic acid halides having 7 to 15 carbon atoms;

(2) a nitrogen-containing organic solvent selected from the groupconsisting of nitrogen-contain ing heterocyclic amines having 5,to 18carbon atoms selected from the pyridine, quinoline and acridine series,saturated aliphatic secondary amines of 2 to 24 carbon atoms, aromaticsecondary amines having 6 to 20 carbon atoms, saturated aliphatictertiary amines having 3 to 18 carbon atoms, aromatic tertiary amineshaving 8 to 30 carbon atoms, aromatic mononitriles having 7 to 15 carbonatoms, aromatic monoisocyanates having 7 to 11 carbon atoms and aromaticazo compounds having 12 to 20 carbon atoms; and

(2) a Si-containing organic solvent selected from the group consistingof tetrahydrocarbylsilanes having saturated alkyl radicals, arylradicals or mixtures thereof of 4 to 50 carbon atoms,tetrahydrocarbylsilanes having an unsaturated alkyl radical of 5 to 28carbon atoms, alkyl hydrogenosilanes of 1 to 30 carbon atoms having anSi-H bond, aryl hydrogenosilanes of 6 to 30 carbon atoms having an Si-Hbond, alkyl halogenosilanes of 3 to 30 carbon atoms having an Si-halogenbond, aryl halogenosilanes of 6 to 30 carbon atoms having an Si-halogenbond, trialkyl silylamines of 6 to 9 carbon atoms, triphenyl silylamine,trimethyl(N methylamino) silane, trimethyl(N diethylamino)silane,saturated alkylsilanes having at least one Si-O-C bond of 2 to 8 carbonatoms, aryl silanes having at least an Si-O-C bond of 9 to 12 carbonatoms, C -C aliphatic mono-or C -C aromatic mono-carboxylic acid estersof trialkyl silanols having 3 to carbon atoms, alkylaryl silanols having8 to carbon atoms or triaryl silanes of 18 to carbon atoms, trialkylsilicon isocyanates having 3 to 10 carbon atoms, dialkyl aryl siliconisocyanates having 8 to 15 carbon atoms, trialkyl silicon isocyanateshaving 18 to 30 carbon atoms, polysilmethylenes of the formula CH SiCH(CH SiCH Si(CH 3 wherein x is an integer of 1 to 10, linear polyalkyl orpolyaryl polysilanes of 6 to 80 carbon atoms, a,-dihaloalkylpolysiloxanes of the formula wherein X is a halogen atom,and

x=1 to 1000, polyalkyl cyclopolysilanes having 12 to 120 carbon atoms,polyaryl cyclopolysilanes having 12 to 120 carbon atoms,organopolysiloxanes of the formula wherein R, R and R"" may be the sameor difftferent and represent an alkyl group having 1 to 4 carbon atoms,an aryl group having 6 to 8 carbon atoms, or hydrogen, and x is aninteger of 1 to 1000, alkyl cyclopolysiloxanes of the formula (RHSiO)wherein R is an alkyl group having 1 to 4 carbon atoms, and y is aninteger of 3 to 8, alkyl cyclopolysiloxanes of the general formula 24wherein R"" is an alkyl group having 1 to 4 carbon atoms, and z is aninteger of 3 to 9, aryl cyclopolysiloxanes of the formula wherein Q isan aryl group having 6 to 8 carbon atoms,

and p is an integer of 3 to 6,

alkyl or aryl polysilazanes of 6 to 50 carbon atoms having an Si-N-Sibond and a molecular weight of not more than 1000; and then separatingsaid extracted titanium trichloride composition from the solventmixture, the amount of said mixed solvent being 1 to parts by weight perpart of the pulverized aluminum-containing titanium trichloridecomponent, and the amount of the solvent (2) or (2) being 0.005- 10.0parts by weight per part of said titanium trichloride component and theamount of solvent,(2)' being 0.005-0.5 part by weight per part of saidtitanium trichloride component; and

(B) an organoaluminum compound selected from the group consisting oftrialkyl aluminum, dialkylaluminum halide, dialkylaluminum alkoxide,alkylaluminum alkoxy halide, reaction products of these with anelectron-donor compound, reaction products of these with an alkali metalcomplex fluoride of a transition metal, reaction products of analkylaluminum dihalide with an electron-donor compound, reactionproducts of an alkylaluminum dihalide with an alkali metal halide, andreaction products of an alkylaluminum dihalide with an alkali metalcomplex fluoride of a transition metal.

2. A catalyst comprising: (A) a titanium trichloride compositionobtained by pulverizing a component consisting of an aluminumcontainingtitanium 'trichloride component prepared by the reduction of titaniumtetrachloride with metallic aluminum, until the ocor 'y-type crystalstructure of said titanium trichloride cannot be identified in the X-raydiffraction pattern, and extracting the resulting titanium trichloridecomposition with a solvent mixture of an inert organic solvent:

(1) selected .from the group consisting of aromatic hydrocarbons having6 to 20 carbon atoms, saturated aliphatic hydrocarbons having 3 to 20carbon atoms, alicyclic hydrocarbons having 3 to 18'carbon atoms,acyclic or cyclic olefins of 2 to 20 carbon atoms, unsaturated aliphatichydrocarbon halides of 2 to 20 carbon atoms, saturated aliphatichydrocarbon halides of l to 20 carbon atoms, halogenated aromatichydrocarbons'having 6 to 16 carbon atoms and carbon disulfide; and amember selected from the group consisting of the following organicsolvents;

(2) an oxygen-containing organic solvent selected from the groupconsisting of saturated aliphatic monoethers having 2 to 32 carbon atomshaving an alkyl radical, aliphatic ethers of 3 to 20 carbon atoms havingat least one unsaturated aliphatic hydrocarbon radical, aromatic ethersof 7 to 16 carbon atoms having a saturated alkyl group or aryl group,monoor diethers having a halogen-substituted aromatic group with 7 to 16carbon atoms, saturated alkyl esters of saturated aliphaticmonocarboxylic acids having a saturated aliphatic monocarboxylic acidresidual group with 1 to 21 carbon atoms and a saturated alkyl groupwith 1 to 16 carbon atoms, unsaturated alkyl esters of saturatedaliphatic monocarboxylic acids having a saturated aliphaticmonocarboxylic acid residual group with 1 to 8 carbon atoms and anunsaturated alkyl group with 2 to 12 carbon atoms, alkyl esters ofunsaturated aliphatic monocarboxylic acids having an unsaturatedaliphatic monocarboxylic acid residual group with 2 to 12 carbon atomsand a saturated or unsaturated alkyl group with 1 to carbon atoms,saturated alkyl esters of aromatic monocarboxylic acids having anaimmatic monocarboxylic acid residual group with 7 to 18 carbon atomsand a saturated alkyl group with 1 to 20 carbon atoms, saturatedaliphatic mono-alcohols having 1 to 18 carbon atoms, monohydric anddihydric phenols having 6 to 16 carbon atoms, saturated aliphaticmonoketones having 3 to 20 carbon atoms, saturated aliphatic diketoneshaving 4 to 12 carbon atoms, aromatic monoketones having 7 to 18 carbonatoms, aromatic monocarboxylic acids having 7 to 18 carbon atoms,saturated aliphatic monocarboxylic acids having 1 to 20 carbon atoms,saturated aliphatic carboxylic acid halides having 2 to 12 carbon atomsand aromatic carboxylic acid halides having 7 to carbon atoms;

(2) a nitrogen-containing organic solvent selected from the groupconsisting of nitrogen-containing heterocyclic amines having 5 to 18carbon atoms selected from the pyridine, quinoline and acridine series,saturated aliphatic secondary amines of 2 to 24 carbon atoms, aromaticsecondary amines having 6 to carbon atoms, saturated aliphatic tertiaryamineshaving 3 to 18 carbon atoms, aromatic tertiary amines having 8 tocarbon atoms, aromatic mononitriles having 7 to 15 carbon atoms,aromatic monoisocyanates having 7 to 11 carbon atoms and aromatic azocompounds having 12 to 20 carbon atoms; and

(2) a Si-containing organic solvent selected from the group consistingof tetrahydrocarbylsilanes having saturated alkyl radicals, arylradicals or mixtures thereof of 4 to 50 carbon atoms,tetrahydrocarbylsilanes having an unsaturated alkyl radical of 5 to 28carbon atoms, alkyl hydrogenosilanes of l to 30 carbon atoms having anSi-H bond, aryl hydrogenosilanes of 6 to 30 carbon atoms having an Si-Hbond, alkyl halogenosilanes of 3 to 30 carbon atoms having an Si-halogenbond, aryl halogenosilanes of 6 to 30 carbon atoms having an Si-halogenbond, trialkyl silylamines of 6 to 9 carbon atoms, triphenyl silylamine,trimethyl(N methylamino) silane, trimethyl(N,N-diethylamino)silane,saturated alkylsilanes having at least one Si-O-C bond of 2 to 8 carbonatoms, aryl silanes having at least an Si-O-C bond of 9 to 12 carbonatoms, C -C aliphatic monoor C -C aromatic mono-carboxylic acid estersof trialkyl silanols having 3 to 10 carbon atoms, alkylaryl silanolshaving 8 to 20 carbon atoms or triaryl silanes of 18 to 30 carbon atoms,trialkyl silicon isocyanates having 3 to 10 carbon atoms, dialkyl arylsilicon isocyanates having 8 to 15 carbon atoms, trialkyl siliconisocyanates having 18 to 30 carbon atoms, polysilmethylenes of theformula CH SiCH (CH SiCI-I Si (CH 3 wherein x is an integer of 1 to 10,linear polyalkyl or polyaryl polysilanes of 6 to 80 carbon atoms, a,wdihaloalkylpolysiloxanes of the formula 26 wherein X is a halogen atomand x=1 to 1000, polyalkyl cyclopolysilanes having 12 to 120 carbonatoms, polyaryl cyclopolysilanes having 12 to 120 carbon atoms,organopolysiloxanes of the formula R(R'R""SiO) SiR wherein R and R"" maybe the same or different and represent an alkyl group having 1 to 4carbon atoms, an aryl group having 6 to 8 carbon atoms, or hydrogen, andx is an integer of 1 to 1000, alkyl cyclopolysiloxanes of the formulawherein R" is an alkyl group having 1 to 4 carbon atoms, and y is aninteger of 3 to 8, alkyl cyclopolysiloxanes of the general formulawherein R"" is an alkyl group having 1 to 4 carbon atoms, and z is aninteger of 3 to 9, aryl cyclopolysiloxanes of the formula (Q2 )p whereinQ is an aryl group having 6 to 8 carbon atoms,

and p is an integer of 3 to 6, alkyl or aryl polysilanzanes of 6 to 50carbon atoms having an Si-N-Si bond and a molecular weight of not morethan 1000; and then separating said extracted titanium trichloridecomposition from the solvent mixture, the amount of the mixed solventbeing 1 to parts by Weight per part of the pulverized aluminumcontainingtitanium trichloride component, and the amount of the solvent (2) or(2)" being 0.005 to 10.0 parts by weight per part of said titaniumtrichloride component and the amount of solvent (2) being 0.0050.5 partsby weight per part of said titanium trichloride component, and (B) anorganoaluminum compound selected from the group consisting of trialkylaluminum, dialkylaluminum halide, dialkylaluminum. alkoxide,alkylaluminum alkoxy halide, reaction products of these with anelectron-donor compound, reaction products of these with an alkali metalcomplex fluoride of a transition metal, reaction products of analkylaluminum dihalide with an electron-donor compound, reaction productof an alkylaluminum dihalide with an alkali metal halide, and reactionproducts of an alkylaluminum dihalide with an alkali metal complexfluoride of a transition metal.

References Cited UNITED STATES PATENTS 3,130,005 4/1964 Siggel et a126094.9 C 3,482,935 12/ 1969 Trementozzi et a1. 26094.9 E 3,032,5105/1962 Tornqvist et al. 26094.9 E 3,365,434 1/ 1968 Coover et al 26094.9C

FOREIGN PATENTS 2,052,525 6/1971 Germany.

7015555 4/1971 Netherlands.

EDWARD J. SMITH, Primary Examiner US. Cl. X.R.

252429 B, 429 C, 93.5 S, 93.7, 94.9 C, 94.9 E

1. IN A PROCESS FOR POLYMERIZING OR COPOLYMERIZING A MONOMER SELECTEDFROM THE GROUP CONSISTING OF ETHYLENE, PROPYLENE, 1-BUTENE,4-METHYL-1-PENTENE, STYRENE, 1-PENTENE, 1-HEXENE AND 3-METHYL-1-BUTENEIN THE PRESENCE OF A CATALYST COMPOSED OF A PULVERIZED TITANIUMTRICHLORIDE COMPONENT AND AN ORGANO-ALUMINUM COMPOUND, THE IMPROVEMENTWHEREIN SAID MONOMER IS POLYMERIZED OR COPOLYMERIZED IN THE PRESENCE OFA CATALYST COMPRISING: (A) A TITANIUM TRICHLORIDE COMPOSITION OBTAINEDBY PULVERIZING A COMPONENT CONSISTING OF AN ALUMINUMCONTAINING TITANIUMTRICHLORIDE COMPONENT PREPARED BY THE REDUCTION OF TITANIUMTETRACHLORIDE WITH METALLIC ALUMINUM, UNTIL THE A- OF V-TYPE CRYSTALSTRUCTURE OF TITANIUM TRICHLORIDE CANNOT BE IDENTIFIED IN THE X-RAYDIFFRACTION PATTERN, AND EXTRACTING THE RESULTING TITANIUM TRICHLORIDECOMPOSITION WITH A SOLVENT MIXTURE OF AN INERT ORGANIC SOLVENT: (1)SELECTED FROM THE GROUP CONSISTING OF AROMATIC HYDROCARBONS HAVING 6 TO20 CARBON ATOMS, SATURATED ALIPHATIC HYDROCARBONS HAVING 3 TO 20 CARBONATOMS, ALICYCLIC HYDROCARBONS HAVING 3 TO 18 CARBON ATOMS, ACYCLIC ORCYCLIC OLEFINS OF 2 20 CARBON ATOMS, UNSATURATED ALIPHATIC HYDROCARBONHALIDES OF 2 TO 20 CARBON ATOMS, SATURATED ALIPHATIC HYDROCARBON HALIDESOF 1 TO 20 CARBON ATOMS, HALOGENATED HALIDES HYDROCARBONS HAVING 6 TO 16CARBON ATOMS AND CARBON DISULFIDE; AND A MEMBER SELECTED FROM THE GROUPCONSISTING OF THE FOLLOWING ORGANIC SOLVENTS; (2) AN OXYGEN-CONTAININGORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF SATURATEDALIPHATIC MONOETHERS HAVING 2 TO 32 CARBON ATOMS HAVING AN ALKYLRADICAL, APHATIC ETHERS OF 3 TO 20 CARBON ATOMS HAVING AT LEAST ONEUNSATURATED ALIPHATIC HYDROCARBON RADICAL, AROMATIC ETHERS OF 7 TO 16CARBON ATOMS HAVING A SATURATED ALKYL OR ARYL RADICAL, MONOETHERS ANDDIETHERS OF 7 TO 16 CARBON ATOMS WHICH ARE HALOGENATED AND CONTAIN ATLEAST ONE AROMATIC RADICAL, SATURATED ALKYL ESTERS OF SATURATEDALIPHATIC MONOCARBOXYLIC ACIDS HAVING AN ALIPHATIC MONOCARBOXYLIC ACIDRESIDUAL GROUP WITH 1 TO 21 CARBON ATOMS AND A SATURATED ALKYL GROUPWITH 1 TO 16 CARBON ATOMS, UNSATURATED ALKYL ESTERS OF SATURATESALIPHATIC MONOCARBOXYLIC ACIDS HAVING A SATURATED ALIPHATICMONOCARABOXYLIC ACID RESIDUAL GROUP WITH 1 TO 8 CARBON ATOMS AND ANUNSATURATED ALKYL GROUP WITH 2 TO12